RU2014130026A - IMPROVEMENT OF FIBER REINFORCED MATERIALS - Google Patents

IMPROVEMENT OF FIBER REINFORCED MATERIALS Download PDF

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RU2014130026A
RU2014130026A RU2014130026A RU2014130026A RU2014130026A RU 2014130026 A RU2014130026 A RU 2014130026A RU 2014130026 A RU2014130026 A RU 2014130026A RU 2014130026 A RU2014130026 A RU 2014130026A RU 2014130026 A RU2014130026 A RU 2014130026A
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polymer
layer
additional
thermoset
prepreg
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RU2014130026A
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Russian (ru)
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RU2615405C2 (en
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Джон ЭЛЛИС
Жан-Марк БЕРО
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Хексел Композитс Лимитед
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B29C70/0035—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties comprising two or more matrix materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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  • Laminated Bodies (AREA)

Abstract

1. Способ получения армированного волокнами термоотверждаемого полимера включающий:(a) пропитывание армирующего волокнистого слоя жидкой термоотверждаемой полимерной композицией с получением препрега, и(b) последующее отверждение термоотверждаемого полимера,где во время пропитывания дополнительный полимерный компонент отдельно вводят в препрег, в термоотверждаемой полимерной композиции не содержится вышеупомянутый дополнительный полимерный компонент помимо термоотверждаемого полимера, и вводятся дополнительные полимеры, которые объединяются с термоотверждаемым полимером в процессе отверждения.2. Способ по п. 1, в котором дополнительный полимер вводят как отдельный слой, тонкий слой или оболочку.3. Способ по п. 1, в котором дополнительный полимер вводят до, во время или после пропитывания армирующего волокнистого слоя термоотверждаемой полимерной композицией.4. Способ по п. 2, в котором оболочка или отдельный слой или тонкий слой представляет собой пленку или тканую или нетканую подложку, или сетку.5. Способ по п. 4, в котором дополнительный полимер представляет собой термопластичный полимер, который не растворяется в термоотверждаемом полимере при комнатной температуре и при повышенных температурах, используемых для отверждения полимера.6. Способ по п. 1, в котором два или более дополнительных полимера вводят как термопластичные слои, полученные из различных термопластичных материалов.7. Способ по п. 6, в котором термопластичные материалы представляют собой полиамиды.8. Способ по п. 5, в котором дополнительные полимеры вводят как слой толщиной от 0,5 до 50 мкм.9. Способ по п. 8, в котором слой имеет пористость, составляющую от 30% до 98%, предпочтите1. A method of producing a fiber-reinforced thermosetting polymer comprising: (a) impregnating the reinforcing fiber layer with a liquid thermosetting polymer composition to produce a prepreg, and (b) subsequent curing of the thermosetting polymer, where, during the impregnation, the additional polymer component is separately introduced into the prepreg, in the thermosetting polymer composition the aforementioned additional polymer component is not contained in addition to the thermoset polymer, and additional polymers are introduced which combined with the thermoset polymer during otverzhdeniya.2. The method according to claim 1, wherein the additional polymer is introduced as a separate layer, thin layer or shell. A method according to claim 1, wherein the additional polymer is introduced before, during or after the impregnation of the reinforcing fiber layer with a thermoset polymer composition. The method of claim 2, wherein the casing or a separate layer or thin layer is a film or a woven or non-woven substrate or mesh. A method according to claim 4, wherein the additional polymer is a thermoplastic polymer that does not dissolve in the thermoset polymer at room temperature and at elevated temperatures used to cure the polymer. The method according to claim 1, wherein two or more additional polymers are introduced as thermoplastic layers obtained from various thermoplastic materials. The method of claim 6, wherein the thermoplastic materials are polyamides. A method according to claim 5, in which additional polymers are introduced as a layer with a thickness of 0.5 to 50 microns. The method of claim 8, wherein the layer has a porosity of 30% to 98%, preferably

Claims (22)

1. Способ получения армированного волокнами термоотверждаемого полимера включающий:1. The method of obtaining fiber-reinforced thermosetting polymer comprising: (a) пропитывание армирующего волокнистого слоя жидкой термоотверждаемой полимерной композицией с получением препрега, и(a) impregnating the reinforcing fiber layer with a liquid thermoset polymer composition to form a prepreg, and (b) последующее отверждение термоотверждаемого полимера,(b) subsequent curing of the thermoset polymer, где во время пропитывания дополнительный полимерный компонент отдельно вводят в препрег, в термоотверждаемой полимерной композиции не содержится вышеупомянутый дополнительный полимерный компонент помимо термоотверждаемого полимера, и вводятся дополнительные полимеры, которые объединяются с термоотверждаемым полимером в процессе отверждения.where, during the impregnation, the additional polymer component is separately introduced into the prepreg, the aforementioned additional polymer component is not contained in the thermoset polymer composition in addition to the thermoset polymer, and additional polymers are introduced which combine with the thermoset polymer during the curing process. 2. Способ по п. 1, в котором дополнительный полимер вводят как отдельный слой, тонкий слой или оболочку.2. The method according to p. 1, in which the additional polymer is introduced as a separate layer, thin layer or shell. 3. Способ по п. 1, в котором дополнительный полимер вводят до, во время или после пропитывания армирующего волокнистого слоя термоотверждаемой полимерной композицией.3. The method according to p. 1, in which the additional polymer is administered before, during or after impregnation of the reinforcing fiber layer with a thermoset polymer composition. 4. Способ по п. 2, в котором оболочка или отдельный слой или тонкий слой представляет собой пленку или тканую или нетканую подложку, или сетку.4. The method according to claim 2, in which the shell or a separate layer or thin layer is a film or a woven or non-woven substrate, or mesh. 5. Способ по п. 4, в котором дополнительный полимер представляет собой термопластичный полимер, который не растворяется в термоотверждаемом полимере при комнатной температуре и при повышенных температурах, используемых для отверждения полимера.5. The method of claim 4, wherein the additional polymer is a thermoplastic polymer that does not dissolve in the thermoset polymer at room temperature and at elevated temperatures used to cure the polymer. 6. Способ по п. 1, в котором два или более дополнительных полимера вводят как термопластичные слои, полученные из различных термопластичных материалов.6. The method according to p. 1, in which two or more additional polymer is introduced as thermoplastic layers obtained from various thermoplastic materials. 7. Способ по п. 6, в котором термопластичные материалы представляют собой полиамиды.7. The method according to claim 6, in which the thermoplastic materials are polyamides. 8. Способ по п. 5, в котором дополнительные полимеры вводят как слой толщиной от 0,5 до 50 мкм.8. The method according to p. 5, in which additional polymers are introduced as a layer with a thickness of 0.5 to 50 microns. 9. Способ по п. 8, в котором слой имеет пористость, составляющую от 30% до 98%, предпочтительно от 50% до 95% и предпочтительнее от 60% до 90%.9. The method of claim 8, wherein the layer has a porosity of from 30% to 98%, preferably from 50% to 95%, and more preferably from 60% to 90%. 10. Способ по п. 9, в котором добавки помимо дополнительных полимеров вводят вместе с дополнительным полимером.10. The method of claim 9, wherein the additives, in addition to the additional polymers, are introduced together with the additional polymer. 11. Способ по п. 10, в котором добавки включают проводящие частицы.11. The method of claim 10, wherein the additives include conductive particles. 12. Способ по п. 1, в котором дополнительный полимер вводят как слой, и волокна в армирующем волокнистом слое являются однонаправленными, и дополнительный полимерный слой удерживает однонаправленные волокна на месте.12. The method of claim 1, wherein the additional polymer is introduced as a layer, and the fibers in the reinforcing fiber layer are unidirectional, and the additional polymer layer holds the unidirectional fibers in place. 13. Способ по п. 12, в котором препрег включает от 25 до 50 масс. % отверждаемого полимера.13. The method according to p. 12, in which the prepreg includes from 25 to 50 mass. % curable polymer. 14. Способ по п. 12, в котором препреги включают от 45 до 75 масс. % волокон.14. The method according to p. 12, in which the prepregs include from 45 to 75 mass. % fiber. 15. Способ по любому из предшествующих пунктов, в котором армированный волокнами термоотверждаемый полимер включает множество пропитанных армирующих волокнистых слоев, которые пропитывают жидкой термоотверждаемой полимерной композицией с получением препрегов, и во время пропитывания вышеупомянутых волокнистых слоев дополнительные полимерные компоненты отдельно вводят в препреги, прокладывая их между вышеупомянутыми препрегами, причем в термоотверждаемой полимерной композиции не содержатся вышеупомянутые дополнительные полимерные компоненты помимо термоотверждаемого полимера, а также вводят дополнительные полимеры, которые объединяются с термоотверждаемым полимером, в процессе отверждения.15. The method according to any one of the preceding claims, wherein the fiber-reinforced thermosetting polymer comprises a plurality of impregnated reinforcing fiber layers that are impregnated with a liquid thermosetting polymer composition to produce prepregs, and during the impregnation of the above-mentioned fiber layers, additional polymer components are separately introduced into the prepregs, laying them between the aforementioned prepregs, wherein the thermoset polymer composition does not contain the aforementioned additional polymers In addition to the thermosetting polymer, the present components also introduce additional polymers that combine with the thermosetting polymer during the curing process. 16. Отверждаемая стопка препрегов, в которой препреги включают армирующий волокнистый слой, пропитанный эпоксидным полимером, в котором не содержатся дополнительные полимеры помимо эпоксидного полимера, и стопка дополнительно включает прокладочные слои, в которых практически не содержатся армирующие волокна, причем, по меньшей мере, один прокладочный слой включает, по меньшей мере, один придающий жесткость термопластичный материал для придания жесткости эпоксидному полимеру.16. A curable stack of prepregs, in which the prepregs include a reinforcing fiber layer impregnated with an epoxy polymer that does not contain additional polymers besides the epoxy polymer, and the stack further includes cushion layers in which there is practically no reinforcing fiber, at least one the cushioning layer includes at least one stiffening thermoplastic material for stiffening the epoxy polymer. 17. Отверждаемая стопка по п. 16, в которой прокладочный слой содержит дополнительные добавки для придания электропроводности конечному многослойному материалу.17. The curable stack according to claim 16, in which the cushioning layer contains additional additives to impart electrical conductivity to the final multilayer material. 18. Отверждаемая стопка по п. 16, в которой каждый препрег имеет водосодержание, составляющее менее чем 15%.18. The curable stack of claim 16, wherein each prepreg has a water content of less than 15%. 19. Отверждаемая стопка по п. 16, имеющая водосодержание, составляющее менее чем 25%.19. The curable stack according to claim 16, having a water content of less than 25%. 20. Препрег или стопка препрегов по любому из пп. 16-19, в котором отверждаемый полимер представляет собой эпоксидный полимер, и полимерная композиция включает полимер, отверждающее вещество и необязательно ускоритель для отверждающего вещества.20. A prepreg or a stack of prepregs according to any one of paragraphs. 16-19, in which the curable polymer is an epoxy polymer, and the polymer composition includes a polymer, a curing agent, and optionally an accelerator for the curing agent. 21. Способ получения препрега, включающий введение одного или нескольких слоев армирующих волокон в контакт с соседним термопластичным полимерным слоем или имеющим открытую структуру листом и приведение в контакт с внешней поверхностью армирующего волокнистого слоя и/или термопластичного полимерного слоя (имеющего открытую структуру листа), причем слой отверждаемого полимера, включает жидкую термоотверждаемую полимерную композицию, в которой не содержатся дополнительные полимеры, и совместное сжатие полимера, волокон и листа для обеспечения, по меньшей мере, частичного заполнения полимером пустот между армирующими волокнами.21. A method of producing a prepreg, comprising bringing one or more layers of reinforcing fibers into contact with an adjacent thermoplastic polymer layer or a sheet having an open structure and contacting the outer surface of the reinforcing fiber layer and / or a thermoplastic polymer layer (having an open sheet structure), wherein the curable polymer layer includes a liquid thermosetting polymer composition that does not contain additional polymers, and joint compression of the polymer, fibers and sheet for both baking, at least partially fill the voids between the reinforcing polymer fibers. 22. Способ по п. 21, в котором армирующий слой волокон расположен между двумя соседними полимерными оболочками перед пропитыванием полимером. 22. The method according to p. 21, in which the reinforcing layer of fibers is located between two adjacent polymer shells before impregnation with the polymer.
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